Organic light emitting diode

ABSTRACT

An organic light emitting diode, including a first electrode; a second electrode facing the first electrode, the second electrode including magnesium; an emission layer between the first electrode and the second electrode; and an electron injection layer between the second electrode and the emission layer, the electron injection layer including a dipole material including a first component and a second component having different polarities, the dipole material including halide, and a content of the magnesium included in the second electrode being in a range of from 10 to 40 volume %.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/281,363, filed Feb. 21, 2019, which is a continuation of U.S. patentapplication Ser. No. 14/821,983, filed Aug. 10, 2015, now U.S. Pat. No.10,236,464, which is a continuation-in-part of U.S. patent applicationSer. No. 14/735,582, filed Jun. 10, 2015, now U.S. Pat. No. 10,003,041,which claims priority to and the benefit of Korean Patent ApplicationNo. 10-2014-0109197, filed Aug. 21, 2014 and Korean Patent ApplicationNo. 10-2015-0099984, filed Jul. 14, 2015, the entire content of all ofwhich is incorporated herein by reference.

BACKGROUND 1. Field

Provided are an organic light emitting diode and an organic lightemitting display device including the same.

2. Description of the Related Art

Lightweight and thin personal computers and televisions sets may requirelightweight and thin display devices, and flat panel displays satisfyingsuch requirements may be substituted for cathode ray tubes (CRTs). Aliquid-crystal display (LCD) is a passive display device, an additionalbacklight as a light source is needed, and an LCD may exhibit a slowresponse time and a narrow viewing angle.

SUMMARY

Embodiments may be realized by providing an organic light emittingdiode, including a first electrode; a second electrode facing the firstelectrode, the second electrode including magnesium; an emission layerbetween the first electrode and the second electrode; and an electroninjection layer between the second electrode and the emission layer, theelectron injection layer including a dipole material including a firstcomponent and a second component having different polarities, the dipolematerial including halide, and a content of the magnesium included inthe second electrode being in a range of from 10 to 40 volume %.

The second electrode may include silver (Ag)-magnesium (Mg), and athickness of the second electrode may be in a range of from 50 to 150 Å.

The first component may include one or more of an alkali metal, analkaline earth metal, a rare earth metal, or a transition metal.

The dipole material may include one or more of LiI, NaI, KI, RbI, CsI,or FrI.

The electron injection layer may further include a metal having a workfunction of 4.0 eV or less, and the metal may include one or more of Li,Na, K, Rb, Cs, Ca, Sr, Ba, Ce, Sm, Eu, Gd, La, Nd, Tb, Lu, Mg, Yb, or analloy thereof.

The electron injecting layer may include a dipole material includingiodine (I) and ytterbium (Yb).

The electron injection layer may be formed by co-depositing a dipolematerial including one of LiI, NaI, KI, RbI, CsI, FrI, and ytterbium(Yb).

The electron injection layer may further include an oxide havingrelative permittivity of 10 or more, and the electron injection layermay be formed by co-depositing two or more of the dipole material, themetal having the work function of 4.0 eV or less, and the oxide havingrelative permittivity of 10 or more.

The organic light emitting diode may further include an electrontransport layer between the emission layer and the electron injectionlayer; and a hole transport layer between the emission layer and thefirst electrode. Each of the hole transport layer and the electrontransport layer may include an organic material.

The emission layer may include a red light emitting layer, a green lightemitting layer, and a blue light emitting layer, and the emission layermay further include an auxiliary layer at a lower end of the blue lightemitting layer.

The organic light emitting diode may further include a red resonanceauxiliary layer at a lower end of the red light emitting layer, and agreen resonance auxiliary layer at a lower end layer of the green lightemission layer.

The auxiliary layer may include a compound represented by ChemicalFormula 1:

wherein each of “A1,” “A2,” and “A3” is an alkyl group, an aryl group,carbazole, dibenzothiophene, dibenzofuran (DBF), or biphenyl, and eachof “a,” “b,” and “c” is an integer in a range of from 0 and 4.

The auxiliary layer may include a compound represented by ChemicalFormula 2:

wherein each of “a,” “b,” and “c” is an integer in a range of from 0 to3, “X” is selected from O, N, and S, and the elements selected for X arethe same as or different from each other.

Embodiments may be realized by providing an organic light emittingdiode, including a first electrode; a second electrode facing the firstelectrode; an emission layer between the first electrode and the secondelectrode; a hole transport region between the first electrode and thesecond electrode; and an electron injection layer between the secondelectrode and the emission layer, the electron injection layer includinga dipole material including a first component and a second componenthaving different polarities, and the hole transport region including adoping layer including a charge generating material.

The doping layer may be adjacent to an interface between the firstelectrode and the hole transport region.

The charge generating material may include a p-dopant.

The p-dopant may include one or more of a quinon derivative, a metaloxide, or a cyano group-containing compound.

The hole transport region may include one or more of a hole injectionlayer or a hole transport layer, and a content of the p-dopant includedin the doping layer may be in a range of 4 volume % or less.

The dipole material may include halide, and the second electrode mayinclude silver-magnesium.

A content of magnesium included in the second electrode may be in arange of from 10 to 40 volume %.

The dipole material may include one more of LiI, NaI, KI, RbI, CsI, orFrI.

The electron injection layer may further include a metal having a workfunction of 4.0 eV or less, and the metal may include one or more of Li,Na, K, Rb, Cs, Ca, Sr, Ba, Ce, Sm, Eu, Gd, La, Nd, Tb, Lu, Mg, Yb, or analloy thereof.

The electron injection layer may include a dipole material includingiodine (I) and ytterbium (Yb)₃.

The electron injection layer may be formed by co-depositing a dipolematerial including one of LiI, NaI, KI, RbI, CsI, FrI, and ytterbium(Yb).

BRIEF DESCRIPTION OF THE DRAWINGS

Features will become apparent to those of skill in the art by describingin detail exemplary embodiments with reference to the attached drawingsin which:

FIG. 1 illustrates a cross-sectional view of an organic light emittingdisplay device according to an exemplary embodiment;

FIG. 2 illustrates an enlarged cross-sectional view of the organic lightemitting diode shown in FIG. 1;

FIG. 3 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2;

FIG. 4 to FIG. 6 illustrate graphs of a voltage-current density in eachof a red pixel, a green pixel, and a blue pixel in the organic lightemitting diode shown in FIG. 2;

FIG. 7 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2;

FIG. 8 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 7;

FIG. 9 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2.

FIG. 10 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2; and

FIG. 11 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2.

DETAILED DESCRIPTION

Example embodiments will now be described more fully hereinafter withreference to the accompanying drawings; however, they may be embodied indifferent forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey exemplary implementations to those skilled in the art.

In the drawings, the thickness and dimensions of layers, films, panels,regions, etc., may be exaggerated for clarity. It will be understoodthat when a layer is referred to as being “on” another layer orsubstrate, it can be directly on the other layer or substrate, orintervening layers may also be present. Further, it will be understoodthat when a layer is referred to as being “under” another layer, it canbe directly under, and one or more intervening layers may also bepresent. In addition, it will also be understood that when a layer isreferred to as being “between” two layers, it can be the only layerbetween the two layers, or one or more intervening layers may also bepresent. Like reference numerals designate like elements throughout thespecification.

FIG. 1 illustrates a cross-sectional view of an organic light emittingdisplay device according to an exemplary embodiment. FIG. 2 illustratesan enlarged cross-sectional view of the organic light emitting diode asshown in FIG. 1.

Referring to FIG. 1 and FIG. 2, the organic light emitting displaydevice according to the exemplary embodiment may include a substrate123, a driving thin film transistor 130, a first electrode 160, alight-emitting element layer 170, and a second electrode 180. The firstelectrode 160 and the second electrode 180 may respectively be an anodeand a cathode, or vice versa.

The substrate 123 may be made of, e.g., an inorganic material such asglass, an organic material such as polycarbonate (PC),polymethylmethacrylate (PMMA), polyethylene terephthalate (PET),polyamide (PA), polyethersulfone (PES), or a combination thereof, or asilicon wafer.

A substrate buffer layer 126 may be formed on the substrate 123. Thesubstrate buffer layer 126 may prevent penetration of impurities andplanarize the surface.

The substrate buffer layer 126 may be made of various materials capableof performing the functions. For example, one of a silicon nitride(SiNx) layer, a silicon oxide (SiOx) layer, and a silicon oxynitride(SiOxNy) layer may be used as the substrate buffer layer 126. In anembodiment, the substrate buffer layer 126 may be omitted according to akind of substrate 123 and a process condition.

A driving semiconductor layer 137 may be formed on the substrate bufferlayer 126. The driving semiconductor layer 137 may be formed of amaterial including polysilicon. The driving semiconductor layer 137 mayinclude a channel region 135 in which impurities (dopants) are notdoped, and a source region 134 and a drain region 136 in which theimpurities are doped at respective sides of the channel region 135. Thedoped ion materials may be P-type impurities such as boron (B), forexample, B₂H₆. The impurities vary according to a kind of thin filmtransistor.

A gate insulating layer 127 made of a silicon nitride (SiNx) or siliconoxide (SiOx) may be formed on the driving semiconductor layer 137. Agate wire including a driving gate electrode 133 may be formed on thegate insulating layer 127. The driving gate electrode 133 may be formedto overlap at least a part of the driving semiconductor layer 137, forexample, the channel region 135.

An interlayer insulating layer 128 covering the driving gate electrode133 may be formed on the gate insulating layer 127. A first contact hole122 a and a second contact hole 122 b exposing the source region 134 andthe drain region 136 of the driving semiconductor layer 137 arerespectively formed in the gate insulating layer 127 and the interlayerinsulating layer 128. The interlayer insulating layer 128 may be formedby using a material such as a silicon nitride (SiNx) or a silicon oxide(SiOx), like the gate insulating layer 127.

A data wire including a driving source electrode 131 and a driving drainelectrode 132 may be formed on the interlayer insulating layer 128. Thedriving source electrode 131 and the driving drain electrode 132 may beconnected with the source region 134 and the drain region 136 of thedriving semiconductor layer 137 through the first contact hole 122 a andthe second contact hole 122 b formed in the interlayer insulating layer128 and the gate insulating layer 127, respectively.

The driving thin film transistor 130 including the driving semiconductorlayer 137, the driving gate electrode 133, the driving source electrode131, and the driving drain electrode 132 may be formed. Theconfiguration of the driving thin film transistor 130 may be variouslymodified.

A planarization layer 124 covering the data wire may be formed on theinterlayer insulating layer 128. The planarization layer 124 may removeand planarize a step, and may increase emission efficiency of theorganic light emitting element to be formed thereon. The planarizationlayer 124 may have a third contact hole 122 c exposing a part of thedrain electrode 132.

The planarization layer 124 may be made of one or more materials of apolyacrylate resin, an epoxy resin, a phenolic resin, a polyamide resin,a polyimide resin, an unsaturated polyester resin, a polyphenylene etherresin, a polyphenylene sulfide resin, or benzocyclobutene (BCB).

In an embodiment, one of the planarization layer 124 and the interlayerinsulating layer 128 may be omitted.

A first electrode of the organic light emitting element, for example, apixel electrode 160, may be formed on the planarization layer 124. Forexample, the organic light emitting diode device may include a pluralityof pixel electrodes 160 which may be disposed for every plurality ofpixels, respectively. The pixel electrodes 160 may be spaced apart fromeach other. The pixel electrode 160 may be connected to the drainelectrode 132 through the third contact hole 122 c of the planarizationlayer 124.

A pixel defining layer 125 having an opening exposing the pixelelectrode 160 may be disposed on the planarization layer 124. Forexample, a plurality of openings respectively corresponding to thepixels may be formed between pixel defining layers 125. Thelight-emitting element layer 170 may be formed for each opening formedby the pixel defining layer 125. Accordingly, a pixel area in which eachlight-emitting element layer 170 may be formed by the pixel defininglayer 125 may be defined.

The pixel electrode 160 may be disposed to correspond to the opening ofthe pixel defining layer 125. In an embodiment, the pixel electrode 160is not disposed only in the opening of the pixel defining layer 125, butmay be disposed below the pixel defining layer 125 so that a part of thepixel electrode 160 overlaps with the pixel defining layer 125.

The pixel defining layer 125 may be made of, for example, resin such asa polyacrylate resin and a polyimide, or a silica-based inorganicmaterial.

The light-emitting element layer 170 may be formed on the pixelelectrode 160. A structure of the light-emitting element layer 170 willbe described below in detail.

The second electrode, for example, a common electrode 180, may be formedon the light-emitting element layer 170. The organic light emittingdiode LD including the pixel electrode 160, the light-emitting elementlayer 170, and the common electrode 180 may be formed.

Each of the pixel electrode 160 and the common electrode 180 may be madeof a transparent conductive material or a transflective or reflectiveconductive material. According to kinds of materials forming the pixelelectrode 160 and the common electrode 180, the organic light emittingdiode device may be a top emission type, a bottom emission type, or adouble-sided emission type.

An overcoat 190 covering and protecting the common electrode 180 may beformed as an organic layer on the common electrode 180.

A thin film encapsulation layer 121 may be formed on the overcoat 190.The thin film encapsulation layer 121 may encapsulate and protect theorganic light emitting element LD and a driving circuit part formed onthe substrate 123 from the external environment.

The thin film encapsulation layer 121 may include organic encapsulationlayers 121 a and 121 c and inorganic encapsulation layers 121 b and 121d which may be alternately laminated. In FIG. 1, as an example, twoorganic encapsulation layers 121 a and 121 c and two inorganicencapsulation layers 121 b and 121 d may be alternately laminated toconfigure the thin film encapsulation layer 121.

Hereinafter, an organic light emitting diode according to an exemplaryembodiment will be described with reference to FIG. 2.

Referring to FIG. 2, the organic light emitting diode according to thepresent exemplary embodiment (i.e., a part X shown in FIG. 1) mayinclude a structure in which a first electrode 160, a hole transportlayer 174, an emission layer 175, an electron transport layer 177, anelectron injection layer 179, and a second electrode 180 may besequentially stacked.

The first electrode 160 may be the anode, may be made of a materialselected from materials having high work functions, and the holeinjection may be made easier. The first electrode 160 may include atransparent electrode and/or a non-transparent electrode. The firstelectrode 160 may be the transparent electrode, and may be formed tohave a thin thickness by using a conductive oxide such as indium tinoxide (ITO), indium zinc oxide (IZO), tin oxide (SnO₂), zinc oxide(ZnO), or a combination thereof, or a metal such as aluminum, silver,and magnesium. The first electrode 160 may be a non-transparentelectrode, and may be formed by using a metal such as aluminum, silverand magnesium.

The first electrode 160 may be formed to have a structure of two or morelayers including different materials. For example, the first electrode160 may be formed to have a structure in which indium tin oxide (ITO),silver (Ag), and indium tin oxide (ITO) may be sequentially stacked.

The first electrode 160 may be formed by using, for example, asputtering method or a vacuum deposition method.

A hole transport region may be positioned on the first electrode 160.The hole transport region may include an auxiliary layer disposedbetween the first electrode and the emission layer 175. The holetransport region may include at least one of a hole transport layer anda hole injection layer. A structure in which the hole transport layer174 is formed in the hole transport region is illustrated in theexemplary embodiment of FIG. 2. The hole transport layer 174 mayfacilitate smooth transport of the holes transferred from the firstelectrode 160. The hole transport layer 174 may include an organicmaterial. For example, the hole transport layer 174 may be formed ofN,N-di(1-naphthyl)-N,N′-di(phenyl)benzidine (NPD),N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl) (TPD), s-TAD, or4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA).

The thickness of the hole transport layer 174 may be in a range of from15 nm to 25 nm. For example, the thickness of the hole transport layer174 may be 20 nm. The emission layer 175 may be disposed on the holetransport layer 174. The emission layer 175 may contain a light emittingmaterial for displaying a predetermined color. For example, the emissionlayer 175 may display a primary color such as blue, green, or red, or acombination thereof.

The thickness of the emission layer 175 may be in a range of from 10 nmto 50 nm. The emission layer 175 may contain a host and a dopant. Theemission layer 175 may contain materials for emitting red, green, blue,and white light, and may be formed by using a phosphorescent or afluorescent material.

The emission layer 175 may emit red light, may contain a host materialincluding carbazole biphenyl (CBP) or 1,3-bis(carbazol-9-yl) (mCP), andmay be formed of a phosphorescent material containing a dopant includingone or more of, for example, PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonate iridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium), or PtOEP (platinumoctaethylporphyrin).

The emission layer 175 may emit green light, may contain a host materialincluding CBP or mCP, and may be formed of a phosphorescent materialcontaining a dopant including Ir(ppy)3(fac-tris(2-phenylpyridine)iridium) or a phosphorescent materialcontaining a dopant including Alq3 (tris(8-hydroxyquinolino)aluminum).

The emission layer 175 may emit green light, may contain a host materialincluding CBP or mCP, and may be formed of a phosphorescent materialcontaining a dopant (4,6-F2ppy)2Irpic. The emission layer 175 may beformed of a phosphorescent material containing one or more ofspiro-DPVBi, spiro-6P, distyryl benzene (DSB), distyryl arylene (DSA), aPFO-based polymer, or a PPV-based polymer.

An electron transport region may be positioned between the emissionlayer 175 and the second electrode 180. The electron transport regionmay include an auxiliary layer disposed between the emission layer 175and the second electrode 180. A structure in which the electrontransport layer 177 and the electron injection layer 179 are formed inthe electron transport region is illustrated in the exemplary embodimentof FIG. 2.

The electron transport layer 177 may be disposed on the emission layer175. The electron transport layer 177 may facilitate transfer ofelectrons from the second electrode 180 to the emission layer 175. Theelectron transport layer 177 may help prevent the holes injected fromthe first electrode 160 from moving to the second electrode 180 throughthe emission layer 175. The electron transport layer 177 may serve as ahole blocking layer, and may improve combination of the holes andelectrons in the emission layer 175.

The electron transport layer 177 may include an organic material. Forexample, the electron transport layer 177 may be formed of one or moreof Alq3 (tris(8-hydroxyquinolino)aluminum), PBD, TAZ, spiro-PBD(2-[4-biphenyl-5-[4-tert-butylphenyl]]-1,3,4-oxadiazole),TAZ(1,2,4-triazole),spiro-PBD(spiro-2-[4-biphenyl-5-[4-tert-butylphenyl]]-1,3,4-oxadiazole),or BAlq(8-hydroxyquinoline beryllium salt).

The electron injection layer 179 may be disposed on the electrontransport layer 177. The electron injection layer 179 may improveelectron injection from the second electrode 180 to the electrontransport layer 177. In the present exemplary embodiment, the electroninjection layer 179 may include a dipole material formed by coupling afirst component and a second component having different polarities. Thefirst component may be an element which may be changed to a positive ionwhen the dipole material is ionized, and the second component may be anelement which may be changed to a negative ion. In the present exemplaryembodiment, the thickness of the electron injection layer 179 may be ina range of from about 2 Å to 25 Å.

The dipole material may have a dipole moment that is higher than that ofLiF. For example, the dipole moment of LiF may be 6.28 Debye, and, inthe present exemplary embodiment, the dipole moment of the dipolematerial may be higher than 6.28 Debye. Referring to the periodic table,the first component of the dipole material may include one or more of analkali metal, an alkaline earth metal, a rare earth metal, or atransition metal, and the second component may include a halogen. Forexample, the first component may include one or more of Li, Na, K, Rb,Cs, Fr, Be, Mg, Ca, Sr, or Ba, the second component may include one ormore of F, Cl, Br, or I, and the dipole material may include one or moreof LiI, NaI, KI, RbI, CsI, or FrI.

The second electrode 180 may be disposed on the electron injection layer179. When the second electrode 180 serves as the cathode, it may includea material having a small work function to make the electron injectioneasy. An example of the material having the small work function mayinclude, for example, a metal such as magnesium, calcium, sodium,potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum,silver, tin, lead, cesium, barium, or an alloy thereof, or a multi-layerstructure substance such as LiF/Al, LiO₂/Al, LiF/Ca, LiF/Al, andBaF₂/Ca. The second electron 180 may include Li, Mg, Al, Al—Li, Ca, Ag,or Mg—Ag.

When the aforementioned second electrode 180 is made of an alloy, analloy ratio may be controlled according to a temperature of a depositionsource, an atmosphere, and a vacuum degree, and it may be selected tohave an appropriate ratio value. In the present exemplary embodiment,the second electrode 180 may have a thickness that is in a range of fromabout 50 to 150 Å. If the thickness of the second electrode 180 issmaller than 50 Å, the difficulty lies in acquiring a surfaceresistance. If the thickness thereof is greater than 150 Å, thereflectivity may be increased, a wide angle distribution (WAD) may bedeteriorated, and a color change in a side view may be caused.

In the present exemplary embodiment, the second electrode 180 may bemade of AgMg, and the Mg content of the second electrode 180 may be in arange of from 10 to 40 volume %.

The second electrode 180 may be configured to have two or more layers.

The following Examples and Comparative Example are provided in order tohighlight characteristics of one or more embodiments, but it will beunderstood that the Examples and Comparative Example are not to beconstrued as limiting the scope of the embodiments, nor is theComparative Example to be construed as being outside the scope of theembodiments. Further, it will be understood that the embodiments are notlimited to the particular details described in the Examples andComparative Example.

Table 1 demonstrates the light efficiency when the electron injectionlayer is made of RbI and CsI according to an exemplary embodiment. InTable 1, Comparative Example 1 indicates a case in which the electroninjection layer was Yb, and Examples 1 and 2 respectively indicate afirst case in which the electron injection layer was made of RbI and asecond case in which the electron injection layer was made of CsI. Thesecond electrode corresponding to a cathode adjacent to the electroninjection layer was AgMg, and the MG content of the negative electrodewas about 25% in Examples 1 and 2. The unit of “%” is volume %. Theelectron injection layer was formed to have a thickness of about 10 Å inExamples 1 and 2.

TABLE 1 B R G efficiency W Incre- efficiency efficiency (CE/y)efficiency ment Comparative 45.8 55.6 106.1 32.1 Ref. Example 1 Example1 50.6 60.1 134.5 37.6 17.1% Example 2 48.7 59.2 133.0 36.5 13.7%

Referring to Table 1, Examples 1 and 2 respectively accomplished whiteefficiencies which were improved by 17.1% and 13.7% as compared withComparative Example 1

Table 2 demonstrates the light efficiency of blue pixels when theelectron injection layer is made of RbI and the negative electrode ismade of AgMg according to an exemplary embodiment. In Table 2, Examples3, 4, 5 and 6 indicate cases in which the MG content of a cathode was10%, 20%, 30% and 40%, respectively. The unit of “%” is volume %. InExamples 3 to 6, the electron injection layer and the negative electrodewere respectively formed to have a thickness of about 10 and 100 Å.

TABLE 2 Mg Driving B efficiency content voltage (candela/ (volume %) (V)ampere/year) Example 3 10 4.2 134.5 Example 4 20 4.1 153.3 Example 5 304.0 144.6 Example 6 40 4.0 142.0

Referring to Table 2, the Mg content may be considered an importantfactor when the negative electrode made of AgMg is formed on theelectron injection layer made of RbI. For example, if the volume % of Mgis smaller than about 10 volume %, the film stability may deteriorate,and electron injection may be difficult. If the volume % is greater thanabout 40 volume %, the electron injection may be too quickly performedto maintain the balance with holes, and the light efficiency may bedeteriorated. Accordingly, in the present exemplary embodiment, the Mgcontent of the second electrode included in the organic light emittingdiode may be in a range of from 10 to 40 volume %.

In the organic light emitting diode LD according to the presentexemplary embodiment, the electron injection layer 179 may include ametal having a work function of 4.0 eV or less and/or an oxide havingrelative permittivity of 10 or more in addition to the dipole material.The electron injection layer 179 may be formed by co-deposition of atleast two of oxides each having relative permittivity of 10 or more andthe metal having the work function of 4.0 eV or less.

In the present exemplary embodiment, examples of the metal having thework function of 4.0 eV or less may include one or more of Li, Na, K,Rb, Cs, Ca, Sr, Ba, Ce, Sm, Eu, Gd, La, Nd, Tb, Lu, Mg, Yb, or an alloythereof. The electron injection layer 179 may be formed as a singlelayer by co-deposition of the metal having the work function of 4.0 eVor less and the dipole material. For example, the electron injectionlayer 179 may be formed by co-deposition of a dipole material includingRbI and a metal including Yb.

Table 3 demonstrates the efficiency when the electron injection layer isformed by co-deposition of RbI doped with Yb according to an exemplaryembodiment. In Comparative Example 1, the electron injection layer wasmade of Yb, and in Examples 7 and 8, the electron injection layer wasmade of RbI doped with Yb and CsI doped with Yb, respectively. A cathodethat was disposed adjacent to the electron injection layer was made ofAgMg, and the Mg content of the cathode in Examples 7 and 8 was 10volume %. In Examples 7 and 8, the electron injection layer was formedto have a thickness of 10 Å.

TABLE 3 B R G efficiency W Incre- efficiency efficiency (CE/y)efficiency ment Comparative 45.8 55.6 106.1 32.1 Ref. Example 1 Example7 61.3 105.3 155 50.4 57.0% Example 8 55 102 150 48.7 51.7%

Referring to Table 3, Examples 7 and 8 respectively accomplished whiteefficiencies which were improved by 57.0% and 51.7% as compared withComparative Example 1.

In the present exemplary embodiment, examples of the oxide havingrelative permittivity of 10 or more may include one or more of WO₃,MoO₃, Cu₂O, Yb₂O₃, Sm₂O₃, Nb₂O₃, Gd₂O₃, or Eu₂O₃.

The organic light emitting diode LD according to an exemplary embodimentmay accomplish smoother electron injection and strong resistance to anexternal oxide or moisture by selectively adding a combination of themetal having the work function of 4.0 eV or less and the oxide havingrelative permittivity of 10 or more into a dipole material having alower dissociation energy and a higher dipole moment than those of LiF.

For example, without being bound by theory, it is believed that, when avoltage is applied to opposite ends of the electrode, a dipole materialof an ion joining state in which positive charges and negative chargesmay be arranged in a dipole thin film (e.g., the electron injectionlayer in the present exemplary embodiment) according to an electricfield. Electrons disposed at an interface between the electron transportlayer 177 and the dipole thin film may be coupled to the dipole materialof the dipole thin film, and holes disposed at an interface between thedipole thin film and the second electrode 180 that may serve as thecathode may be coupled to the dipole material of the dipole thin film.Many surplus electrons or holes as the offset amount for voltagemaintenance may exist in the interface between the electron transportlayer 177 and the dipole thin film or between the dipole thin film andthe second electrode 180. A material like RbI included in the electroninjection layer 179 according to the present exemplary embodiment may bea polar molecule having dipole moments without an electric field. Thedipole moments may be present at a larger number, and electrons or holesto be coupled to the dipole material at the interface may exist at alarger number. Thus, a larger amount of electrons or holes may bepresent in the interface. For example, the interface of the organicelectron transport layer 177 which may be positively charged bygathering holes may be represented as spaces at which electrons may beremoved, which may indicate many empty spaces to which electrons maymove. A vacuum level of the interface of the organic electron transportlayer 177 may be shifted (a LUMO level may be decreased), and aninjection barrier may be lowered. The metal having the work function of4.0 eV or less may serve as a positively charged interface, for example,due to an electron donor characteristic, and the electron injectioncharacteristic may be further improved.

FIG. 3 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2.

In the present exemplary embodiment, the thickness of the electroninjection layer 179 may be adjusted in order to keep a balance betweenthe electron injection characteristic improved by forming the electroninjection layer 179 by use of a dipole material and the hole injectioncharacteristic that may be relatively weakened. Table 4 shows results ofmeasuring the driving voltage and the light efficiency that were changedby varying the thickness of the electron injection layer 179 made of RbIas 10 Å, 20 Å, 30 Å, 40 Å, and 50 Å. The Mg content of the cathode madeof AgMg was about 20 volume %.

TABLE 4 Driving Light voltage efficiency Rbl_10/AgMg, 4.1 153.3 20%Rbl_20/AgMg, 4.1 148 20% Rbl_30/AgMg, 4.2 142 20% Rbl_40/AgMg, 4.3 13520% Rbl_50/AgMg, 4.5 110 20%

RbI may serve as an inorganic dipole material or a dielectric material,and tunneling may be employed as the electron injection mechanism. Asshown in Table 4, as the thickness of RbI is increased, electrontunneling may be reduced, the electron injection characteristic may beweakened, the charge balance may be broken, and an increase in thedriving voltage and a decrease in the efficiency may be caused.

The hole transport region according to the present exemplary embodimentmay further include charge generating materials to improve conductivity.These charge generating materials may be uniformly or non-uniformlydispersed in the hole transport region. In the present exemplaryembodiment, the hole transport region may contact the first electrode160, and the charge generating materials may be doped and deposed to beadjacent to an interface between the hole transport region and the firstelectrode 160. In the present exemplary embodiment, since the holetransport layer 174 contacts the first electrode 160, the chargegenerating materials may be formed to be adjacent to the interfacebetween the hole transport layer 174 and the first electrode 160.Referring to FIG. 3, a doping layer 174 p at which the charge generatingmaterials are doped and deposed is disposed at a lower end portion ofthe hole transport layer 174 facing the first electrode 160. The contentof a p-dopant included in the doping layer 174 p according to thepresent exemplary embodiment may be equal to or smaller than about 4volume %, for example, may be equal to or smaller than about 1 volume %.

The charge generating material according to the present exemplaryembodiment may serve to improve charge balance between electrons andholes when the light efficiency is increased by the action of theelectron injection layer including the dipole material.

In the present exemplary embodiment, the charge generating materials maybe p-dopants, for example, the p-dopants may be, for example, one ormore of a quinon derivative, a metal oxide, or a cyano group-containingcompound.

Examples of the p-dopant may include one or more of a quinon derivativesuch, for example, as tetracyanoquino-dimethan (TCNQ) ortetrafluoro-tetracyano-1,4-benzoquinondimethane (F4TCNQ) represented byChemical Formula A, a metal oxide such as, for example, a tungsten oxideor a molybdenum oxide, or a compound represented by Chemical Formula B.

When the electron injection is significantly quickly performed in theelectron transport region by forming the electron injection layer by useof a dipole material, re-combination of the electrons and the holes maynot be performed at the emission layer 175. Accordingly, there-combination of the electrons and the holes may be performed, and theefficiency may be reduced. In a front surface resonant structure of theorganic light emitting diode, a thickness thereof in a red pixel areamay be thickest, and the distance at which holes reach the emissionlayer 175 may be relatively longest. As a result, in the red pixel area,as the content of the p-dopants is increased, the balance of the holeswhich was not maintained, for example, due to a relatively small numberthereof, may be restored, and the driving voltage and the efficiency maybe improved as shown in Table 5.

TABLE 5 P-dopant Driving Light Content Voltage (V) Efficiency p-dopant1% 5.5 21.6 p-dopant 2% 5.4 25.3 p-dopant 3% 4.6 50.2 p-dopant 4% 4.561.3 p-dopant 5% 5.3 23.2

The hole transport layer according to the present exemplary embodimentmay further include one or more of a hole injection layer, a bufferlayer, or an electron blocking layer as well as the hole transportlayer. The hole injection layer may be formed on the hole transportlayer. This will be described later in detail with reference to FIG. 7.

The buffer layer may serve to increase a light emission efficiency bycompensating an optical resonance distance according to a wavelength oflight emitted from the emission layer. Materials that may be included inthe hole transport region may be employed as materials included in thebuffer layer. The electron blocking layer may serve to prevent electroninjection from an electron transport region which will be describedlater.

FIG. 4 to FIG. 6 illustrate graphs of a voltage-current density in eachof a red pixel, a green pixel, and a blue pixel in the organic lightemitting diode shown in FIG. 2.

In FIG. 4 to FIG. 6, in Comparative Experimental Example 1 the electroninjection layer was made of Yb, in Experimental Example 1 the electroninjection layer was made of RbI, and in Experimental Example 7 theelectron injection layer was made of RbI.

Referring to FIG. 4 to FIG. 6, an electron injection rate was increasedin Experimental Examples 1 and 7, in which the electron injection layerwas made of RbI or RbI:Yb, from the point that Experimental Examples 1and 2 show a low threshold voltage (Vth) and a steep inclination ascompared with Comparative Experimental Example 1.

FIG. 7 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2;

For example, FIG. 7 illustrates a structure in which a hole injectionlayer 172 may be added into the hole transport region of the organiclight emitting diode LD in the exemplary embodiment of FIG. 2. In thepresent exemplary embodiment, the hole injection layer 172 may bedisposed between the hole transport layer 174 and the first electrode160. The hole injection layer 172 may facilitate easier injection ofholes from the first electrode 160 to the hole transport layer 174. Inthe present exemplary embodiment, the hole injection layer 172 mayinclude a dipole material in which a metal or a non-metal having a workfunction of 4.3 eV or more and a halogen may be combined. In anembodiment, the hole injection layer 172 may be formed of an inorganicmaterial or an organic material.

The metal or the non-metal having the work function of 4.3 eV or moremay include one or more of Ag, Au, B, Be, C, Co, Cr, Cu, Fe, Hg, Ir, Mo,Nb, Ni, Os, Pd, Pt, Re, Rh, Ru, Sb, Se, Si, Sn, Ta, Te, Ti, V, W, or Zn.

The description made with reference to FIG. 2 other than theaforementioned difference is applicable to the modification of FIG. 7.

FIG. 8 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 7.

The hole transport region according to the present exemplary embodimentmay further include charge generating materials to improve conductivity.These charge generating materials may be uniformly or non-uniformlydispersed in the hole transport region. In the present exemplaryembodiment, the hole transport region may contact the first electrode160, and the charge generating materials may be doped and deposed to beadjacent to an interface between the hole transport region and the firstelectrode 160. In the present exemplary embodiment, since the holetransport layer 174 contacts the first electrode 160, the chargegenerating materials may be formed to be adjacent to the interfacebetween the hole transport layer 172 and the first electrode 160.Referring to FIG. 3, a doping layer 172 p at which the charge generatingmaterials are doped and deposed is disposed at a lower end portion ofthe hole transport layer 172 facing the first electrode 160. The contentof a p-dopant included in the doping layer 172 p according to thepresent exemplary embodiment may be equal to or smaller than about 4volume %, for example, may be equal to or smaller than about 1 volume %.

The charge generating material according to the present exemplaryembodiment may serve to improve charge balance between electrons andholes when the light efficiency is increased by the action of theaforementioned electron injection layer including the dipole material.

Examples of the charge generating materials according to the presentexemplary embodiment may be the same as those described in the exemplaryembodiment of FIG. 3.

As described above, the hole transport layer according to the presentexemplary embodiment may further include one or more of a hole injectionlayer, a buffer layer, or an electron blocking layer as well as the holetransport layer.

The buffer layer may serve to increase a light emission efficiency bycompensating an optical resonance distance according to a wavelength oflight emitted from the emission layer. Materials that may be included inthe hole transport region may be employed as materials included in thebuffer layer. The electron blocking layer may serve to prevent electroninjection from an electron transport region which will be describedlater

FIG. 9 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2.

For example, FIG. 9 illustrates the same structure as that of theorganic light emitting diode LD in the exemplary embodiment of FIG. 2,except that the electron injection layer 179 may be formed to have twolayers. In the present exemplary embodiment, the electron injectionlayer 179 may include a first electron injection layer 179-1 and asecond electron injection layer 179-2. Each of the first electroninjection layer 179-1 and the second electron injection layer 179-2 maybe formed by using at least one of a dipole material having a firstcomponent and a second component which have different polarities, ametal having a work function of 4.0 eV or less, and an oxide havingrelative permittivity of 10 or more, or by co-deposition of thesematerials. The first electron injection layer 179-1 and the secondelectron injection layer 179-2 may be formed of the same material, ormay include different materials.

The description made with reference to FIG. 2 other than theaforementioned difference is applicable to the modification of FIG. 9.

FIG. 10 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2.

For example, FIG. 10 illustrates the same structure as that of theorganic light emitting diode LD in the exemplary embodiment of FIG. 2,except that the electron injection layer 179 may be formed to have threelayers. In the present exemplary embodiment, the electron injectionlayer 179 may include a first electron injection layer 179-1, a secondelectron injection layer 179-2, and a third electron injection layer179-3. Each of the first electron injection layer 179-1, the secondelectron injection layer 179-2, and the third electron injection layer179-3 may be formed by using at least one of a dipole material having afirst component and a second component which have different polarities,a metal having a work function of 4.0 eV or less, and an oxide havingrelative permittivity of 10 or more, or by co-deposition of at least twoof these materials. The first electron injection layer 179-1, the secondelectron injection layer 179-2, and the third electron injection layer179-3 may be formed of the same material, or may include differentmaterials.

The description made with reference to FIG. 2 other than theaforementioned difference is applicable to the modification of FIG. 8.

FIG. 11 illustrates a cross-sectional view of a modification of theorganic light emitting diode shown in FIG. 2.

For example, FIG. 11 illustrates a modification of the emission layer175 in the organic light emitting diode LD of FIG. 2. In the presentexemplary embodiment, the emission layer 175 may include a red emissionlayer R, a green emission layer G, a blue emission layer B, and anauxiliary layer BIL for increasing efficiency of the blue light emittinglayer B disposed at a lower end thereof.

The thickness of the red light emitting layer R may be in a range offrom about 30 nm to about 50 nm, the thickness of the green lightemitting layer G may be in a range of from about 10 nm to about 30 nm,and thickness of the blue light emitting layer B may be in a range offrom about 10 nm to about 30 nm. The thickness of the auxiliary layerBIL may be about 20 nm. The auxiliary layer BIL may serve to adjust ahole charge balance, and may improve the efficiency of the blue lightemitting layer B. The auxiliary layer BIL may contain a compound that isrepresented by the following Chemical Formula 1.

In Chemical Formula 1, each of “A1,” “A2,” and “A3” may be an alkylgroup, an aryl group, carbazole, dibenzothiophene, dibenzofuran (DBF),or biphenyl, and each of “a,” “b,” and “c” may be an integer in a rangeof from 0 to 4.

Examples of compounds represented by the chemical formula 1 may includethe following Chemical Formulae 1-1, 1-2, 1-3, 1-4, 1-5, and 1-6.

According to an exemplary embodiment, the auxiliary layer BIL maycontain a compound that is represented by the following Chemical Formula2.

In Chemical Formula 2, each of “a,” “b,” and “c” may be an integer in arange of from 0 to 3, “X” may be selected from O, N, and S, and theelements selected for X may be the same as or different from each other.

Examples of compounds represented by Chemical Formula 2 may include thefollowing Chemical Formulae 2-1 to 2-6.

According to an exemplary embodiment, the auxiliary layer BIL maycontain a compound that is represented by the following Chemical Formula3.

In Chemical Formula 3, “A1” may be an alkyl group, an aryl group,carbazole, dibenzothiophene, or dibenzofuran (DBF), and each of L1 andL2 may be

n being an integral in a range of from 0 to 3. The DBF connected to L1and L2 may be substituted with carbazole or dibenzothiophene.

Hereinafter, a synthesis method of the auxiliary layer BIL according toan exemplary embodiment will be described. As one example, the synthesismethod of Chemical Formula 1-1 will be described.

Synthesis Example

Under an argon atmosphere, 6.3 g of 4-dibenzofuranboronic acid, 4.8 g of4,4′,4″-tribromotriphenylamine, 104 mg oftetrakis(triphenylphosphine)palladium (Pd(PPh₃)₄), 48 ml of a 2Msolution of sodium carbonate (Na₂CO₃), and 48 ml of toluene were putinto a 300 ml three-neck flask, and then they were reacted at atemperature of 80° C. for 8 hours. The reaction liquid was extracted byusing toluene and water, and the extract was dried by using sodiumsulfate anhydrous. The resultant mixture was concentrated under areduced pressure, and a crude product obtained was refined through acolumn purifying process, thereby obtaining 3.9 g of a whitish yellowpowder.

In FIG. 11, a red resonance auxiliary layer R′ may be disposed below thered light emission layer R, and a green resonance auxiliary layer G′ maybe disposed below the green light emission layer G. The red resonanceauxiliary layer R′ and the green resonance auxiliary layer G′ are layersthat set a resonant distance (a resonance distance) for a respective oneof the colors (e.g., red or green). In some embodiments, a blueresonance auxiliary layer is not included. For example, a separateresonance auxiliary layer disposed between the hole transport layer 174and the blue light emission layer B and the auxiliary layer BIL may notbe formed below the blue light emission layer B and the auxiliary layerBIL corresponding to the red light emission layer R or the green lightemission layer G. In some embodiments, the auxiliary layer BILphysically may contact the hole transport layer 174.

Although not shown in FIG. 11, the hole injection layer 172 may beformed between the first electrode 160 and the hole transport layer 174as in the exemplary embodiment described with reference to FIG. 7.

The description made with reference to FIG. 2 other than theaforementioned difference is applicable to the modification of FIG. 11.

By way of summation and review, an organic light emitting display deviceas a display device may have a wide viewing angle, outstanding contrast,and a fast response time. The organic light emitting display device mayinclude an organic light emitting diode for emitting light, and, in theorganic light emitting diode device, electrons injected from oneelectrode and holes injected from another electrode may be combined witheach other in an emission layer, excitons may be generated, energy maybe outputted from the excitons, and light may be emitted.

Provided are an organic light emitting diode and an organic lightemitting display device including the same, which may exhibit highefficiency and a long lifespan. According to an exemplary embodiment, itmay be possible to increase light emitting efficiency by forming theelectron injection layer including a dipole material. According to anexemplary embodiment, it may be possible to increase light emittingefficiency of the blue emission layer by forming an auxiliary layerbelow the blue emission layer.

Example embodiments have been disclosed herein, and although specificterms are employed, they are used and are to be interpreted in a genericand descriptive sense only and not for purpose of limitation. In someinstances, as would be apparent to one of skill in the art as of thefiling of the present application, features, characteristics, and/orelements described in connection with a particular embodiment may beused singly or in combination with features, characteristics, and/orelements described in connection with other embodiments unless otherwisespecifically indicated. Accordingly, it will be understood by those ofskill in the art that various changes in form and details may be madewithout departing from the spirit and scope of the present invention asset forth in the following claims.

What is claimed is:
 1. A light emitting diode comprising: a firstelectrode; a second electrode facing the first electrode, the secondelectrode including magnesium and silver; an emission layer between thefirst electrode and the second electrode, the emission layer including ablue light emitting layer; and an electron injection layer between thesecond electrode and the emission layer, wherein the electron injectionlayer includes a dipole material and Yb, wherein the dipole materialincludes one or more of LiI, NaI, KI, RbI, CsI, or FrI, and wherein acontent of the silver included in the second electrode is greater than acontent of the magnesium included in the second electrode.
 2. The lightemitting diode as claimed in claim 1, further comprising: an electrontransport layer between the emission layer and the electron injectionlayer; and a hole transport layer between the emission layer and thefirst electrode, wherein each of the hole transport layer and theelectron transport layer includes an organic material.
 3. The lightemitting diode as claimed in claim 2, further comprising a doping layeradjacent to the hole transport layer.
 4. The light emitting diode asclaimed in claim 3, wherein the doping layer comprises a chargegenerating material including a p-dopant.
 5. The light emitting diode asclaimed in claim 4, wherein the p-dopant includes one or more of aquinone derivative, a metal oxide, or a cyano group-containing compound.6. The light emitting diode as claimed in claim 5, wherein a content ofthe p-dopant included in the doping layer is in a range of 4 volume % orless.
 7. The light emitting diode as claimed in claim 1, wherein acontent of the magnesium included in the second electrode is in a rangeof from 10 to 30 volume %.
 8. The light emitting diode as claimed inclaim 1, further comprising an auxiliary layer between the firstelectrode and the emission layer.
 9. The light emitting diode as claimedin claim 8, wherein the auxiliary layer includes a compound representedby Chemical Formula 1:

wherein each of “A1,” “A2,” and “A3” is an alkyl group, an aryl group,carbazole, dibenzothiophene, dibenzofuran (DBF), or biphenyl, and eachof “a,” “b,” and “c” is an integer in a range of from 0 to
 4. 10. Thelight emitting diode as claimed in claim 1, further comprising a dopinglayer between the first electrode and the second electrode, wherein thedoping layer includes charge generating material.
 11. The light emittingdiode as claimed in claim 1, wherein a thickness of the second electrodeis in a range of from 50 to 150 Å.
 12. The light emitting diode asclaimed in claim 1, wherein the electron injection layer is formed byco-depositing a dipole material including one of LiI, NaI, KI, RbI, CsI,and FrI, and Yb.
 13. The light emitting diode as claimed in claim 1,wherein the electron injection layer is formed by co-depositing two ormore of the dipole material and a metal having a work function of 4.0 eVor less.